WO2008042384A1 - Polyester fiber compositions - Google Patents
Polyester fiber compositions Download PDFInfo
- Publication number
- WO2008042384A1 WO2008042384A1 PCT/US2007/021178 US2007021178W WO2008042384A1 WO 2008042384 A1 WO2008042384 A1 WO 2008042384A1 US 2007021178 W US2007021178 W US 2007021178W WO 2008042384 A1 WO2008042384 A1 WO 2008042384A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- polyester fiber
- renewable
- molecular weight
- crystalline
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Definitions
- thermoplastic, high molecular weight polyester resin fibers comprising renewable components.
- Such fibers find utility in flooring applications including carpet fibers, non-woven fiber mats, and reinforcing fibers.
- the thermoplastic, polyester resin has a number average molecular weight (Mn) of a least 5,000, and in other embodiments the polyester resins have a molecular weight (Mn) of at least 10,000.
- the polyester resin from which fibers are formed comprise aromatic and aliphatic diacid components and aliphatic diol components.
- the aromatic diacid component is terephthalic acid.
- an amount of phthalic acid, phthalic anhydride or isophthalic acid may be used in combination with the terephthalic acid to control the crystalline melt temperature - Tm. In some cases an amount of trimellitic anhydride may also be used.
- the aliphatic diacid and diol components preferably come from renewable sources and have a Biobased Content.
- Renewable aliphatic diacid and aliphatic diol components may include but are not limited to Bio-PDO (1,3-propanediol), 1,4-butanediol, sebacic acid, succinic acid, adipic acid, azelaic acid, glycerin and citric acid.
- these materials may also be modified by reaction with epoxidized soybean, epoxidized linseed oil, or other natural oils, or by being mixed with epoxidized soybean, epoxidized linseed oil, or other natural oils.
- the polyesters may be pre-reacted with epoxidized natural oils, or the reaction can by a dynamic vulcanization.
- Dynamic vulcanization is the process of intimate melt mixing of a thermoplastic polymer and a suitable reactive rubbery polymer to generate a thermoplastic elastomer. These reactions are particularly of interest for acid terminated polyesters.
- the diol components may also include diols which are branched or hindered to modify crystallinity in the final polyester fiber. These can include neopentyl glycol and glycerin.
- renewable components based on plants, animals, or biomass processes have a different radioactive C 14 signature than those produced from petroleum. These renewable, biobased materials have carbon that comes from contemporary (non-fossil) biological sources. A more detailed description of biobased materials is described in a paper by Ramani Narayan, "Biobased & Biodegradable Polymer Materials: Rationale, Drivers, and Technology Exemplars,” presented at American Chemical Society Symposium, San Diego 2005; American Chemical Society Publication #939, June 2006.
- the Biobased Content is defined as the amount of biobased carbon in the material or product as fraction weight (mass) or percent weight (mass) of the total organic carbon in the material or product.
- ASTM D6866 (2005) describes a test method for determining Biobased content.
- the high molecular weight polyester resin is crystalline and comprises a crystalline melting temperature Tm between about 100 0 C and 150 0 C. In yet another embodiment, the polyester has a Tm greater than about 150 0 C. In yet another embodiment, the polyester resin has a Tm of at least 190 0 C. In another embodiment, the polyester compositions include modifying traditional thermoplastic aromatic polyester resins useful as fibers by the addition of an amount of a renewable aliphatic diacid to help control crystalline regions and Tm.
- thermoplastic, high molecular weight polyester resin may also be branched.
- aliphatic alcohols that have more than two functional groups, such as glycerin, or aromatic acids having more than two functional groups such as trimellitic anhydride may be used to produce branched polyesters.
- thermoplastic, high molecular weight polyesters via known transesterification techniques.
- the high molecular weight polyesters may be prepared by several known methods.
- One method involves esterification of a diacid and a diol components at elevated temperature. Typically, an excess of diol is employed (see Example IA). After essentially all of the acid functional groups have reacted, a high vacuum is applied and excess diol is stripped off during transesterification, thereby increasing molecular weight.
- the diacid components comprise a mixture of aromatici diacid and renewable aliphatic diacid components.
- renewable 1,3-PDO is the diol of choice to build high molecular weight in this step of the process.
- high molecular weight polyester resin can be made by esterification of a diacid and diol at elevated temperature using an excess of diacid (See example IB). After all the hydroxyl groups are reacted, a high vacuum is applied to build molecular weight. The mechanism by which high molecular weight is achieved is not clear.
- polyester co-reaction resin product had a Tm between 100 0 C and about 150 0 C.
- the polyester co-reaction resin product has a Tm greater than about 150 0 C. In yet another embodiment, the polyester co-reaction resin product has a Tm greater than 190 0 C. It is obvious that these transesterification reactions may be carried out on virgin PET, PPT or PBT resin if desired.
- polyester resins were determined by Gel Permeation Chromatography (GPC) using the following procedure.
- the polyester resin was dissolved into THF, quantitatively diluting to -30 mg/ml and filtering with a 0.45 micron filter. Two drops of toluene were added to each sample solution as an internal flow rate marker.
- UC Universal Calibration
- MW is absolute (not relative only to standards).
- the mobile phase for the THF soluble samples was THF at 1.0 ml/min.
- the data was processed using the Viscotek OmniSec UC software.
- the instrument is calibrated using a series of polystyrene narrow standards. To verify calibration, secondary standards were run. They include a 250,000 MW polystyrene broad standard, and a 90,000MW PVC resin.
- Areaj The area of the i lh slice of polymer distribution
- M 1 The molecular weight of the i lh slice of polymer distribution
- Polydispersity (Pd) a number value used to describe the molecular weight distribution and is obtained by Mw
- Fibers can be prepared from the above described polyester resins by any well known technique, including melt spinning techniques. Optimization of fiber physical properties by orientation and annealing techniques may also be employed. These fibers can be subsequently utilized in the manufacture of carpet products, non-woven fiber webs, and as reinforcing fibers.
- IA This example describes the general procedure utilized to make thermoplastic, high molecular weight polyesters from diacids and diols.
- a desired polyester formulation was developed based upon mole equivalent weight of the diacid and diol functional groups.
- An excess of diol of the most volatile diol component of the formulation was employed in the formulation.
- 1,3-propanediol is the excess diol of choice.
- the diacid and diol ingredients were added into a stainless steel vessel of a RCl automated reactor (Mettler-Toledo Inc, 1900 Polaris Parkway, Columbus, Ohio), stirred and heated under a continuous flow of pure, dry nitrogen.
- the ingredients were heated to 200 0 C for 2 hours and temperature increased to 23O 0 C for an additional 4 to 6 hours until essentially all acid end groups were reacted and theoretical amount of water removed. Subsequently, the nitrogen was stopped and a high vacuum was applied. The mixture was heat and stirred under high vacuum for an additional 4 or more hours at 230 0 C to 300 0 C. In some cases the temperature of the transesterification step was increased to 250 0 C or higher. Depending upon the experiment, a vacuum in the range of 5 mm of mercury was utilized. Subsequently, the polymer was allowed to cool to 150 0 C to 200 0 C and physically removed from the reactor under a flow of nitrogen and allowed to cool to room temperature.
- diacid components are described above, it is understood that their simple diesters such as from methanol or ethanol can be used to prepare the thermoplastic polyester resin via known transesterification techniques.
- the polyesters from this procedure generally have ester terminated end groups.
- IB The same general procedure as in IA is employed. A desired polyester formulation was developed based upon mole equivalent weight of the diacid and diol functional groups. An excess of around 0.01 to 0.5 mole excess of diacid was typically employed in the formulation. The ingredients were mixed and heated as in IA above, except that the temperature was generally held below 200 0 C to keep acid/anhydride from being removed until all hydroxyl groups were reacted. Subsequently, a high vacuum was applied as in IA and the mixture heated to 23O 0 C and 280 0 C and stirred as in Example IA. The resultant high molecular weight polyester was removed from the reactor and cooled as in IA.
- the following formulation was processed as per Example IA to prepare the aliphatic polyester EX-I comprising 100% renewable components and a Biobased Content of 100%.
- the aliphatic polyester EX-I was mixed with clear PET bottle recycle resin obtained from Nicos Polymers & Grinding of Nazareth, Pa., and catalyst added as listed below.
- Example IIA Example IIA
- the resultant polyester having 50% renewable content and 50% recycle content was shown to have a molecular weight Mn of 17,200 with a Tg of -9°C and a Tm of 114 0 C.
- Molecular weight Mn of the starting PET recycle bottle resin was determined by GPC techniques described above and found to be 14,000.
- a sample of PET film obtained from Nicos Polymers & Grinding was also analyzed by GPC and molecular weight Mn determined to be 17,300.
- Example 3 Additional Polyesters Made by Transesterification Between High Molecular Weight Aliphatic, Renewable Polyesters and Recycle Polyester Resin.
- polyesters of Table 2A were each mixed with recycle PET bottle resin obtained from Nicos Polymers & Grinding of Nazareth, Pa, and 0.1% T-20 catalyst added and transesterification conducted as per Example 1.
- transesterification was also carried out on PBT resin Celanex 1600A obtained from Ticona (formerly Hoechst Celanese Corp.), Summit, NJ.
- Table 2B shows some of the resultant polyester co-reaction products and their Tm.
- the Tm of the resultant co-reaction product can be controlled by the ratio of the recycle polyester resin and the co-reactant polyester resin. It is obvious that these transesterification co-reactions may be carried out on virgin PET or PBT type resin.
- Co-reacted polyesters with higher Tm may be produced by using less renewable, aliphatic polyester than described in the Table 2B above.
- the melting points listed in Table 2B were determined using an "Optimelt" automated unit.
- Theoretical Biobased Content was calculated for the above co-reacted products.
- the Biobased Content ranged from 56.5% to 58.3% for the 50:50 blends, and 35.8% to 37.5% for the 70:30 blends.
- the Biobased Content can be varied from about 5% by weight to 95% by weight.
- non-recycled, virgin PET, PBT and PPT can be used instead of the recycled PET.
- the renewable resin should be at least 5% by weight.
- Tm crystalline melting point
- degree of crystallinity in the polyesters useful as fibers, is to modify the traditional high Tm polyester fiber resins by incorporating aliphatic diacids into the polymer.
- any aliphatic diacid can be employed, it is preferred to utilize a diacid from renewable resources that has a Biobased Content.
- Two series of high molecular weight polyesters (Table 4A and 4B) were prepared according to Example IA.
- Tm listed in Table 3 A were determined the same as Example 2 using the Optimelt automated unit.
- the series of high molecular weight polyesters of Table 3B was also prepared as per Example IA. This table shows that Tm can be controlled by the addition of renewable diacid as described above, as well as addition of aromatic diacids that breakup the crystallinity of the resultant polyester.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic, high molecular weight polyester resin fibers comprise renewable components. Such fibers find utility in flooring applications including carpet fibers, non-woven fiber mats, and reinforcing fibers.
Description
Polyester Fiber Compositions
This invention describes thermoplastic, high molecular weight polyester resin fibers comprising renewable components. Such fibers find utility in flooring applications including carpet fibers, non-woven fiber mats, and reinforcing fibers.
In some embodiments, the thermoplastic, polyester resin has a number average molecular weight (Mn) of a least 5,000, and in other embodiments the polyester resins have a molecular weight (Mn) of at least 10,000.
In one embodiment, the polyester resin from which fibers are formed comprise aromatic and aliphatic diacid components and aliphatic diol components. In one embodiment the aromatic diacid component is terephthalic acid. In some embodiments, an amount of phthalic acid, phthalic anhydride or isophthalic acid may be used in combination with the terephthalic acid to control the crystalline melt temperature - Tm. In some cases an amount of trimellitic anhydride may also be used.
The aliphatic diacid and diol components preferably come from renewable sources and have a Biobased Content. Renewable aliphatic diacid and aliphatic diol components may include but are not limited to Bio-PDO (1,3-propanediol), 1,4-butanediol, sebacic acid, succinic acid, adipic acid, azelaic acid, glycerin and citric acid. To further increase the renewable content and to improve other properties, these materials may also be modified by reaction with epoxidized soybean, epoxidized linseed oil, or other natural oils, or by being mixed with epoxidized soybean, epoxidized linseed oil, or other natural oils.
The polyesters may be pre-reacted with epoxidized natural oils, or the reaction can by a dynamic vulcanization. Dynamic vulcanization is the process of intimate melt mixing of a thermoplastic polymer and a suitable reactive rubbery polymer to generate a thermoplastic elastomer. These reactions are particularly of interest for acid terminated polyesters.
Other diacid and diol components from renewable resources will become available as the need for renewable materials continues to grow. The diol components may also include diols which are branched or hindered to modify crystallinity in the final polyester fiber. These can include neopentyl glycol and glycerin.
Renewable components based on plants, animals, or biomass processes have a different radioactive C14 signature than those produced from petroleum. These renewable, biobased
materials have carbon that comes from contemporary (non-fossil) biological sources. A more detailed description of biobased materials is described in a paper by Ramani Narayan, "Biobased & Biodegradable Polymer Materials: Rationale, Drivers, and Technology Exemplars," presented at American Chemical Society Symposium, San Diego 2005; American Chemical Society Publication #939, June 2006.
The Biobased Content is defined as the amount of biobased carbon in the material or product as fraction weight (mass) or percent weight (mass) of the total organic carbon in the material or product. ASTM D6866 (2005) describes a test method for determining Biobased content.
In one embodiment, the high molecular weight polyester resin is crystalline and comprises a crystalline melting temperature Tm between about 1000C and 1500C. In yet another embodiment, the polyester has a Tm greater than about 1500C. In yet another embodiment, the polyester resin has a Tm of at least 1900C. In another embodiment, the polyester compositions include modifying traditional thermoplastic aromatic polyester resins useful as fibers by the addition of an amount of a renewable aliphatic diacid to help control crystalline regions and Tm.
The thermoplastic, high molecular weight polyester resin may also be branched. For example, utilizing aliphatic alcohols that have more than two functional groups, such as glycerin, or aromatic acids having more than two functional groups such as trimellitic anhydride may be used to produce branched polyesters.
Although, the above diacid components are described, it is understood that their simple diesters such as from methanol or ethanol can be used to prepare the thermoplastic, high molecular weight polyesters via known transesterification techniques.
The high molecular weight polyesters may be prepared by several known methods. One method involves esterification of a diacid and a diol components at elevated temperature. Typically, an excess of diol is employed (see Example IA). After essentially all of the acid functional groups have reacted, a high vacuum is applied and excess diol is stripped off during transesterification, thereby increasing molecular weight. In some embodiments the diacid components comprise a mixture of aromatici diacid and renewable aliphatic diacid components. In some embodiments, renewable 1,3-PDO is the diol of choice to build high molecular weight in this step of the process.
It has also found that high molecular weight polyester resin can be made by esterification of a diacid and diol at elevated temperature using an excess of diacid (See example IB). After all
the hydroxyl groups are reacted, a high vacuum is applied to build molecular weight. The mechanism by which high molecular weight is achieved is not clear.
Another method for obtaining high molecular weight polyesters involves the co-reaction of a renewable polyester with recycle polyesters such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PPT (polypropylene terephthalate) or other polyester resins. In these co-reactions an aliphatic polyester comprising renewable ingredients was first prepared as described in Example 1. In one embodiment, the aliphatic polyester has a Biobased Content of 100%. The recycle polyester resin was then mixed with the aliphatic polyester and transesterification between the two polyesters was accomplished at high temperature and preferably under high vacuum. In one embodiment^ the polyester co-reaction resin product had a Tm between 1000C and about 1500C. In another embodiment, the polyester co-reaction resin product has a Tm greater than about 1500C. In yet another embodiment, the polyester co-reaction resin product has a Tm greater than 1900C. It is obvious that these transesterification reactions may be carried out on virgin PET, PPT or PBT resin if desired.
Molecular weight of the polyester resins was determined by Gel Permeation Chromatography (GPC) using the following procedure. The polyester resin was dissolved into THF, quantitatively diluting to -30 mg/ml and filtering with a 0.45 micron filter. Two drops of toluene were added to each sample solution as an internal flow rate marker.
Samples soluble in THF were run by the following conditions. GPC analysis was run on the TriSec instrument using a four column bank of columns with pore sizes: 106, 2 mixed D PLGeI and 500 Angstroms. Three injections were made for the sample and calibration standards for statistical purposes. Universal Calibration (UC) GPC was used to determine MW. UC is a GPC technique that combines Refractive Index (RI) detection (conventional GPC) with Intrinsic Viscometry (IV) detection. Advantages of UC over conventional GPC are:
1. MW is absolute (not relative only to standards).
2. Yields information about branching of molecules.
The mobile phase for the THF soluble samples was THF at 1.0 ml/min. The data was processed using the Viscotek OmniSec UC software. The instrument is calibrated using a series of polystyrene narrow standards. To verify calibration, secondary standards were run. They include a 250,000 MW polystyrene broad standard, and a 90,000MW PVC resin. The calculated molecular weight averages are defined as follows:
• Mn = ∑ ( Area 1
∑(Areaj) / (M1 )
• Mw = ∑ r (Area,) X (M,) 1
Σ(Areai)
• M2 = ∑ r (Area;)2 X (M1) 1
∑.[ (ArCa1) X (M1) I
Areaj = The area of the ilh slice of polymer distribution M1 = The molecular weight of the ilh slice of polymer distribution
Polydispersity (Pd) = a number value used to describe the molecular weight distribution and is obtained by Mw
Mn
Highly crystalline or some high molecular weight samples insoluble in THF were dissolved in a 50/50 (wt.) mixture of tetrachloroethylene (TTCE)/phenol. The column set is 104 and 500 Angstrom 50cm Jordi columns. The mobile phase was 50/50 (wt.) mixture of TTCE/phenol at 0.3 ml/min. flow rate. The slower flow rate is due to the greater back pressure of the solvent system on the columns. The data was processed using the Viscotek UC OmniSec software.
Since MW data must be compared from one column set to the other, standards and selected samples were run on both column sets in THF for comparison. A calibration curve was made for each column set. There is good agreement of the standards between the two sets.
Fibers can be prepared from the above described polyester resins by any well known technique, including melt spinning techniques. Optimization of fiber physical properties by orientation and annealing techniques may also be employed. These fibers can be subsequently utilized in the manufacture of carpet products, non-woven fiber webs, and as reinforcing fibers.
Example 1. Procedure For Preparation of High Molecular Weight Polyesters From Diacids and Diols
IA: This example describes the general procedure utilized to make thermoplastic, high molecular weight polyesters from diacids and diols. A desired polyester formulation was developed based upon mole equivalent weight of the diacid and diol functional groups. An excess of diol of the most volatile diol component of the formulation was employed in the formulation. In one embodiment, 1,3-propanediol is the excess diol of choice. The diacid and diol ingredients were added into a stainless steel vessel of a RCl automated reactor (Mettler-Toledo Inc, 1900 Polaris Parkway, Columbus, Ohio), stirred and heated under a
continuous flow of pure, dry nitrogen. Typically, the ingredients were heated to 2000C for 2 hours and temperature increased to 23O0C for an additional 4 to 6 hours until essentially all acid end groups were reacted and theoretical amount of water removed. Subsequently, the nitrogen was stopped and a high vacuum was applied. The mixture was heat and stirred under high vacuum for an additional 4 or more hours at 2300C to 3000C. In some cases the temperature of the transesterification step was increased to 2500C or higher. Depending upon the experiment, a vacuum in the range of 5 mm of mercury was utilized. Subsequently, the polymer was allowed to cool to 1500C to 2000C and physically removed from the reactor under a flow of nitrogen and allowed to cool to room temperature.
It is understood that removal of the volatile diol component during transesterification leads to high molecular weight. High molecular weight may be obtained faster if higher vacuum (below 1 mm of mercury) is utilized. It is also known that as the melt viscosity increases due to increased molecular weight, the removal of diol becomes more difficult. The increase in molecular weight can become diffusion dependent because of the high viscosity of the molten polyester. This means that the released volatile diol from the transesterification reaction reacts back into the polymer before it can diffuse out of the melt, and be removed. Renewing the surface of the melt can facilitate the loss of diol and increase molecular weight. The polyesters obtained from this procedure generally have terminal hydroxyl end groups.
Although, diacid components are described above, it is understood that their simple diesters such as from methanol or ethanol can be used to prepare the thermoplastic polyester resin via known transesterification techniques. The polyesters from this procedure generally have ester terminated end groups.
IB: The same general procedure as in IA is employed. A desired polyester formulation was developed based upon mole equivalent weight of the diacid and diol functional groups. An excess of around 0.01 to 0.5 mole excess of diacid was typically employed in the formulation. The ingredients were mixed and heated as in IA above, except that the temperature was generally held below 2000C to keep acid/anhydride from being removed until all hydroxyl groups were reacted. Subsequently, a high vacuum was applied as in IA and the mixture heated to 23O0C and 2800C and stirred as in Example IA. The resultant high molecular weight polyester was removed from the reactor and cooled as in IA.
The mechanism of achieving high molecular weight is not clear. In some formulations containing phthalic acid or anhydride, phthalic anhydride was identified as being removed from the mixture. The use of a nitrogen sparge below the surface of the molten polyester
during the vacuum step also helped produce high molecular weight polyesters. The polyesters obtained from this procedure generally have terminal acid end groups.
Example 2. Preparation of High Molecular Weight Polyesters by Co-Reaction With Recycle Crystalline Polyesters
The following formulation was processed as per Example IA to prepare the aliphatic polyester EX-I comprising 100% renewable components and a Biobased Content of 100%.
Table IA
The aliphatic polyester EX-I was mixed with clear PET bottle recycle resin obtained from Nicos Polymers & Grinding of Nazareth, Pa., and catalyst added as listed below.
Table IB
The mixture was heated and stirred under nitrogen at 265°C for a period of about 3 hours, and a high vacuum applied as in Example IA for an additional 3 hours at 265°C. Subsequently, the resultant polyester having 50% renewable content and 50% recycle content was shown to have a molecular weight Mn of 17,200 with a Tg of -9°C and a Tm of 1140C. Molecular weight Mn of the starting PET recycle bottle resin was determined by GPC techniques described above and found to be 14,000. A sample of PET film obtained from Nicos Polymers & Grinding was also analyzed by GPC and molecular weight Mn determined to be 17,300.
Example 3. Additional Polyesters Made by Transesterification Between High Molecular Weight Aliphatic, Renewable Polyesters and Recycle Polyester Resin.
High molecular weight, renewable polyesters comprising the compositions of Table 2A were made according to Example IA.
Table 2A
The polyesters of Table 2A, were each mixed with recycle PET bottle resin obtained from Nicos Polymers & Grinding of Nazareth, Pa, and 0.1% T-20 catalyst added and transesterification conducted as per Example 1. In some examples, transesterification was also carried out on PBT resin Celanex 1600A obtained from Ticona (formerly Hoechst Celanese Corp.), Summit, NJ. Table 2B shows some of the resultant polyester co-reaction products and their Tm. The Tm of the resultant co-reaction product can be controlled by the ratio of the recycle polyester resin and the co-reactant polyester resin. It is obvious that these transesterification co-reactions may be carried out on virgin PET or PBT type resin.
Table 2B
Co-reacted polyesters with higher Tm may be produced by using less renewable, aliphatic polyester than described in the Table 2B above. The melting points listed in Table 2B were determined using an "Optimelt" automated unit. Theoretical Biobased Content was calculated for the above co-reacted products. The Biobased Content ranged from 56.5% to 58.3% for the 50:50 blends, and 35.8% to 37.5% for the 70:30 blends. The Biobased Content can be varied from about 5% by weight to 95% by weight.
Of course, non-recycled, virgin PET, PBT and PPT can be used instead of the recycled PET. In that case, the renewable resin should be at least 5% by weight.
Example 3. Aromatic/ Aliphatic Crystalline Polyester Preparation
Another approach to control the crystalline melting point (Tm) and degree of crystallinity in the polyesters useful as fibers, is to modify the traditional high Tm polyester fiber resins by incorporating aliphatic diacids into the polymer. Although any aliphatic diacid can be employed, it is preferred to utilize a diacid from renewable resources that has a Biobased Content. Two series of high molecular weight polyesters (Table 4A and 4B) were prepared according to Example IA.
Table 3A
*cyclohexane dimethanol
Tm listed in Table 3 A were determined the same as Example 2 using the Optimelt automated unit.
The series of high molecular weight polyesters of Table 3B was also prepared as per Example IA. This table shows that Tm can be controlled by the addition of renewable diacid as described above, as well as addition of aromatic diacids that breakup the crystallinity of the resultant polyester.
Table 3B
**The crystalline melting temperatures listed in Table 3B were determined by Differential Scanning Calorimetry (DSC) techniques.
The series of high molecular weight polyesters of Table 3C was also prepared as per Example IA. This table shows that Tm can be controlled by the addition of renewable diacid as described above.
Table 3C
"cyclohexane dimethanol
Claims
1. A crystalline polyester fiber comprising an aromatic diacid component and a renewable aliphatic diacid component.
2. The polyester fiber of Claim 1, further comprising a renewable diol component.
3. The polyester fiber of Claim 1, wherein the melting point of the crystalline polyester is greater than 1000C.
4. The polyester fiber of Claim 3, wherein the melting point of the crystalline polyester is greater than 1500C.
5. The polyester fiber of Claim 4, wherein the melting point of the crystalline polyester is greater than 1900C.
6. The polyester fiber of Claim 1, wherein the aromatic diacid comprises terephthalic acid.
7. The polyester fiber of Claim 1, wherein the renewable aliphatic diacid is selected from the group consisting of sebacic acid, succinic acid, adipic acid, azelaic acid, citric acid, and mixtures thereof.
8. The polyester fiber of Claim 2, wherein the renewable diol component is selected from the group consisting of to Bio-PDO (1,3-propanediol), 1,4-butanediol, glycerin, and mixtures thereof.
9. The polyester fiber of Claim 1, wherein the polyester fiber has a Biobased Content of at least about 5%.
10. The polyester fiber of Claim 9, wherein the polyester fiber has a Biobased Content of at least about 50%.
11. A crystalline polyester fiber comprising the co-reaction product of a crystalline polyester resin and a polyester resin having a renewable component.
12. The polyester fiber of Claim 11, wherein the polyester fiber has a Biobased Content of at least about 5%.
13. The polyester fiber of Claim 12, wherein the polyester fiber has a Biobased Content of at least about 50%.
14. The crystalline polyester fiber of Claim 11, wherein the crystalline polyester resin comprises a recycle polyester resin.
15. The polyester fiber of Claim 11, wherein the melting point of the crystalline polyester is greater than 1000C.
16. The polyester fiber of Claim 15, wherein the melting point of the crystalline polyester is greater than 1500C.
17. The polyester fiber of Claim 16, wherein the melting point of the crystalline polyester is greater than 1900C.
18. The polyester fiber of Claim 14, wherein the polyester resin comprises at least 98% renewable components and recycle components.
19. The polyester fiber of Claim 1, wherein the polyester resin has a number average molecular weight (Mn) of at least 5,000.
20. The polyester fiber of Claim 1, wherein the polyester resin has a number average molecular weight (Mn) of at least 10,000.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US84876206P | 2006-10-02 | 2006-10-02 | |
US60/848,762 | 2006-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008042384A1 true WO2008042384A1 (en) | 2008-04-10 |
Family
ID=39268771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/021178 WO2008042384A1 (en) | 2006-10-02 | 2007-10-02 | Polyester fiber compositions |
Country Status (2)
Country | Link |
---|---|
US (1) | US20080081898A1 (en) |
WO (1) | WO2008042384A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US9828461B2 (en) | 2012-03-01 | 2017-11-28 | Sabic Global Technologies B.V. | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7888405B2 (en) * | 2004-01-30 | 2011-02-15 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
KR20110112339A (en) | 2008-12-15 | 2011-10-12 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Copolyesters with enhanced tear strength |
US20110213056A1 (en) * | 2008-12-15 | 2011-09-01 | E.I. Du Pont De Nemours And Company | Copolyesters with enhanced tear strength |
US8796356B2 (en) | 2009-09-23 | 2014-08-05 | Sabic Innovative Plastics Ip B.V. | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
TW201124101A (en) * | 2009-11-02 | 2011-07-16 | Morgan Collection Inc | Knitted fabric bed skirt |
TWM379415U (en) * | 2010-01-12 | 2010-05-01 | Yi Yu Wang Entpr Co Ltd | Massage glove for shower |
EP2580284A4 (en) | 2010-06-09 | 2015-04-22 | Mannington Mills | Floor covering composition containing renewable polymer |
US8629236B2 (en) * | 2010-09-28 | 2014-01-14 | Axalta Coating Systems Ip Co., Llc | Polyester having renewable 1,3-propanediol |
US9970155B2 (en) | 2013-03-05 | 2018-05-15 | Nike, Inc. | Acid dyeing of polyurethane materials |
CN107459631B (en) * | 2016-12-07 | 2019-03-22 | 金发科技股份有限公司 | A kind of polyester terephthalate -co- sebacate resin and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2891930A (en) * | 1957-03-25 | 1959-06-23 | Eastman Kodak Co | Fiber-forming polyesters from trans-1, 4-cyclohexanedicarboxylic compounds and 1, 1-cyclohexane dimethanol |
US5340846A (en) * | 1993-01-29 | 1994-08-23 | Amoco Corporation | Increased throughput in melt fabrication and foaming of polyester |
US5349028A (en) * | 1992-05-11 | 1994-09-20 | Showa Highpolymer Co., Ltd. | Polyester fibers |
US20060106167A1 (en) * | 2004-11-12 | 2006-05-18 | Shah Pankaj V | Moisture-reactive hot-melt compositions |
Family Cites Families (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2851436A (en) * | 1955-09-26 | 1958-09-09 | Armstrong Cork Co | Method of making dhsocyanate-modified polyester with polymerized vinyl halide |
FR1506864A (en) * | 1966-01-03 | 1967-12-22 | Monsanto Co | Terrazzo type paving and similar coverings |
US3718715A (en) * | 1971-05-19 | 1973-02-27 | Du Pont | Blends of thermoplastic copolyester elastomers with vinyl chloride polymers |
US3991005A (en) * | 1971-11-22 | 1976-11-09 | Wallace Richard A | Structural material and method |
US3972962A (en) * | 1973-10-23 | 1976-08-03 | Emery Industries, Inc. | Non-migrating polymeric plasticizers for polyvinyl chloride |
US4011358A (en) * | 1974-07-23 | 1977-03-08 | Minnesota Mining And Manufacturing Company | Article having a coextruded polyester support film |
US4083824A (en) * | 1977-04-20 | 1978-04-11 | Armstrong Cork Company | Non-vinyl surface covering composition |
JPS5610451A (en) * | 1979-07-05 | 1981-02-02 | Toray Industries | Resin coated metallic plate for vessel |
US4400468A (en) * | 1981-10-05 | 1983-08-23 | Hydrocarbon Research Inc. | Process for producing adipic acid from biomass |
US4614556A (en) * | 1984-04-16 | 1986-09-30 | Armstrong World Industries, Inc. | Method for making decorative product |
US4595626A (en) * | 1985-01-28 | 1986-06-17 | Armstrong World Industries, Inc. | Conformable tile |
US4820763A (en) * | 1985-08-08 | 1989-04-11 | The B. F. Goodrich Company | Poly(vinyl chloride) polyblend containing a crystalline polyester with limited miscibility and reinforced composites thereof |
US5244942A (en) * | 1987-12-19 | 1993-09-14 | Huels Troisdorf Ag | Homogenous, particularly multicolor-structured synthetic resin sheet or panel, as well as process for its production |
US5391612A (en) * | 1989-11-03 | 1995-02-21 | Armstrong World Industries, Inc. | Halogen-free resilient flooring |
US5576367A (en) * | 1990-01-03 | 1996-11-19 | Henkel Corporation | Polyester gasket plasticizers suitable for use with internally plasticized appliance coatings |
US5276082A (en) * | 1990-07-13 | 1994-01-04 | Armstrong World Industries, Inc. | Halogen-free floor covering |
US6495656B1 (en) * | 1990-11-30 | 2002-12-17 | Eastman Chemical Company | Copolyesters and fibrous materials formed therefrom |
DE4135937C2 (en) * | 1991-10-31 | 1997-07-03 | Pegulan Tarkett Ag | Process for making latex, PVC, and plasticizer-free textile or plastic floor and wall coverings |
US5458953A (en) * | 1991-09-12 | 1995-10-17 | Mannington Mills, Inc. | Resilient floor covering and method of making same |
AU7622594A (en) * | 1993-09-20 | 1995-04-10 | Amtico Company Limited, The | Floor coverings |
US5434217A (en) * | 1994-03-04 | 1995-07-18 | E. I. Du Pont De Nemours And Company | Flexible polar thermoplastic polyolefin compositions |
GB9415930D0 (en) * | 1994-08-04 | 1994-09-28 | Forbo Nairn Ltd | Floor coverings |
US5997782A (en) * | 1994-10-17 | 1999-12-07 | "debolon" dessauer bodenbelage GmbH | Multi-component composite material and method for producing a laminar multi-component composite material from a halogen compound-free flexible plastic |
KR100352738B1 (en) * | 1994-11-30 | 2003-03-15 | 타키론 가부시기가이샤 | Merchant |
SE503631C2 (en) * | 1995-09-15 | 1996-07-22 | Tarkett Ab | Halogen-free flooring material |
DE19548681C2 (en) * | 1995-12-23 | 1998-01-22 | Pegulan Tarkett Ag | Process for the production of foamed layers from polyolefin on calenders |
US6617008B1 (en) * | 1996-02-22 | 2003-09-09 | Idemitsu Petrochemical Co., Ltd. | Decorative film or sheet, and decorative material and building material made by using the same |
CA2189198C (en) * | 1996-04-08 | 2003-12-30 | Sten-Ake Blomkvist | Floorcovering material |
US6224804B1 (en) * | 1996-06-14 | 2001-05-01 | Dlw Aktiengesellschaft | Low-emission elastomer floor covering |
US6254956B1 (en) * | 1996-09-04 | 2001-07-03 | The Dow Chemical Company | Floor, wall or ceiling covering |
US5753767A (en) * | 1996-12-13 | 1998-05-19 | Armstrong World Industries, Inc. | Polymer composition suitable as resilient flooring or welding rod |
WO1998038245A1 (en) * | 1997-02-28 | 1998-09-03 | The Dow Chemical Company | Filled polyethylene compositions |
US5945472A (en) * | 1997-02-28 | 1999-08-31 | Armstrong World Industries, Inc. | Highly-filled chlorine-free surface covering |
US6285788B1 (en) * | 1997-06-13 | 2001-09-04 | Sharp Laboratories Of America, Inc. | Method for fast return of abstracted images from a digital image database |
US5973049A (en) * | 1997-06-26 | 1999-10-26 | The Dow Chemical Company | Filled polymer compositions |
EP1002014A1 (en) * | 1997-08-08 | 2000-05-24 | The Dow Chemical Company | Sheet materials suitable for use as a floor, wall or ceiling covering material, and processes and intermediates for making the same |
US6017586A (en) * | 1998-02-19 | 2000-01-25 | Catalyst Group, Inc. | Polymer material and method of making same utilizing inert atmosphere |
JP3947641B2 (en) * | 1998-10-02 | 2007-07-25 | 株式会社Djk | Method for producing polyester resin foam molding |
WO2000023518A1 (en) * | 1998-10-16 | 2000-04-27 | Nitto Boseki Co., Ltd. | Interior resin article |
US6291725B1 (en) * | 2000-03-03 | 2001-09-18 | Board Of Trustees Operating Michigan State University | Catalysts and process for hydrogenolysis of sugar alcohols to polyols |
EP1160269A3 (en) * | 2000-05-30 | 2002-01-23 | Nippon Shokubai Co., Ltd. | Biodegradable recycled polyester resin and production process therefor |
US6573340B1 (en) * | 2000-08-23 | 2003-06-03 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials |
US6617376B2 (en) * | 2001-03-30 | 2003-09-09 | Crane Plastics Company Llc | Flexible wood composition |
US6911263B2 (en) * | 2002-01-30 | 2005-06-28 | Awi Licensing Company | PET wear layer/sol gel top coat layer composites |
US6921791B2 (en) * | 2002-05-07 | 2005-07-26 | Awi Licensing Company | Thermoplastic elastomer |
US6869985B2 (en) * | 2002-05-10 | 2005-03-22 | Awi Licensing Company | Environmentally friendly polylactide-based composite formulations |
US7256223B2 (en) * | 2002-11-26 | 2007-08-14 | Michigan State University, Board Of Trustees | Environmentally friendly polylactide-based composite formulations |
US20040197515A1 (en) * | 2003-04-03 | 2004-10-07 | Shultz Jeffrey R. | Tile having a non-directional visual appearance |
US7029750B2 (en) * | 2003-07-14 | 2006-04-18 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition and production method thereof |
US7232605B2 (en) * | 2003-07-17 | 2007-06-19 | Board Of Trustees Of Michigan State University | Hybrid natural-fiber composites with cellular skeletal structures |
US7927859B2 (en) * | 2003-08-22 | 2011-04-19 | Rice University | High molar succinate yield bacteria by increasing the intracellular NADH availability |
US7175904B2 (en) * | 2003-08-28 | 2007-02-13 | Congoleum Corporation | Non-vinyl flooring and method for making same |
US20050079780A1 (en) * | 2003-10-14 | 2005-04-14 | Rowe Richard E. | Fiber wear layer for resilient flooring and other products |
US20050137921A1 (en) * | 2003-12-22 | 2005-06-23 | Shahriari Shahram P. | Method for evaluating the costs and benefits of environmental construction projects |
US7160977B2 (en) * | 2003-12-22 | 2007-01-09 | Eastman Chemical Company | Polymer blends with improved notched impact strength |
US20050164023A1 (en) * | 2004-01-26 | 2005-07-28 | Davis Scott M. | Structurally reinforced resinous article and method of making |
JP4418721B2 (en) * | 2004-08-20 | 2010-02-24 | 株式会社堀場製作所 | Nitrogen compound analyzer |
-
2007
- 2007-10-02 WO PCT/US2007/021178 patent/WO2008042384A1/en active Application Filing
- 2007-10-02 US US11/906,474 patent/US20080081898A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2891930A (en) * | 1957-03-25 | 1959-06-23 | Eastman Kodak Co | Fiber-forming polyesters from trans-1, 4-cyclohexanedicarboxylic compounds and 1, 1-cyclohexane dimethanol |
US5349028A (en) * | 1992-05-11 | 1994-09-20 | Showa Highpolymer Co., Ltd. | Polyester fibers |
US5340846A (en) * | 1993-01-29 | 1994-08-23 | Amoco Corporation | Increased throughput in melt fabrication and foaming of polyester |
US20060106167A1 (en) * | 2004-11-12 | 2006-05-18 | Shah Pankaj V | Moisture-reactive hot-melt compositions |
Non-Patent Citations (1)
Title |
---|
KURIAN: "A new polymer platform for the future - Sorona from Corn derived 1,3-porpanediol", JOURNAL OF POLYMERS & THE ENVIRONMENT, vol. 13, no. 2, April 2005 (2005-04-01), pages 159 - 167, XP019283638 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
US9487621B2 (en) | 2011-08-30 | 2016-11-08 | Sabic Global Technologies B.V. | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
US9487625B2 (en) | 2012-03-01 | 2016-11-08 | Sabic Global Technologies B.V. | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
US9828461B2 (en) | 2012-03-01 | 2017-11-28 | Sabic Global Technologies B.V. | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
Also Published As
Publication number | Publication date |
---|---|
US20080081898A1 (en) | 2008-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2008042384A1 (en) | Polyester fiber compositions | |
WO2008042386A2 (en) | Polyester binder for flooring products | |
AU2007305234B2 (en) | PVC/polyester binder for flooring | |
KR101989045B1 (en) | Biodegradable resin composition having excellent weather resistance and storage stability and the method of manufacturing the same | |
US10934390B2 (en) | Polyester polyols with increased clarity | |
Kint et al. | Synthesis, characterization, and properties of poly (ethylene terephthalate)/poly (1, 4-butylene succinate) block copolymers | |
CN107257814B (en) | Biodegradable copolyester composition | |
Pepic et al. | Synthesis and characterization of biodegradable aliphatic copolyesters with poly (ethylene oxide) soft segments | |
CN112048058A (en) | Preparation method of high-melting-point crystalline biodegradable copolyester | |
CN113993926A (en) | Biodegradable resin composition having improved mechanical properties, moldability and weather resistance, and process for producing the same | |
US20030060596A1 (en) | Amorphous copolyesters | |
US6531548B1 (en) | Blends of poly(1,3-propylene 2,6-naphthalate) | |
CN115558092A (en) | Recycling method of waste PET and biodegradable copolyester prepared by adopting recycling method | |
CN113929886A (en) | Long-chain branched PETG copolyester and preparation method thereof | |
AU2014203157B2 (en) | Polyester binder for flooring products | |
JP5082287B2 (en) | Biomass particles and method for producing the same | |
JP4152767B2 (en) | Polyester block copolymer and method for producing the same | |
CN113493598B (en) | Biodegradable polyester and preparation method thereof | |
CN113956449B (en) | Multifunctional graphene polyester and preparation method thereof | |
JPH11279268A (en) | Polyester block copolymer and its production | |
Panagiotopoulos et al. | Recycling/Upcycling of Physically Aged Poly (butylene succinate) into PBS Vitrimers through Zn (II)-Catalyzed Melt Vitrimerization | |
CN114763406A (en) | Novel copolyesters and their use | |
WO2023111923A1 (en) | A biodegradable polymer and a process for its preparation | |
TW202227526A (en) | Biodegradable polyester and method for preparing the same | |
AU2013200973A1 (en) | Polyester binder for flooring products |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07839157 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07839157 Country of ref document: EP Kind code of ref document: A1 |